Excited Singlet State Of Porphyrin Research Articles

Boosting Transport Distances for Molecular Excitons within Photoexcited Metal-Organic Framework Films.

Herein, we describe the fabrication of porphyrin-containing metal-organic framework thin films with 1,4-diazabicyclo[2.2.2]octane (DABCO) pillaring linkers and investigate exciton transport within the films. Steady-state emission spectroscopy indicates that the exciton can traverse up to 26 porphyrin layers when DABCO is used as a pillaring linker, whereas on average only 9-11 layers can be traversed when either 4,4'-bipyridine (a pillaring linker) or pyridine (a nonpillaring, layer-interdigitating ligand) is used. These results can be understood by taking into account the decreased separation distances between transition dipoles associated with chromophores (porphyrins) sited in adjacent layers. Shorter distances translate into faster Förster-type exciton hopping and, therefore, more hops within the few nanosecond lifetime of the porphyrin's singlet excited-state. The findings have favorable implications for the development of MOF-based photoelectrodes and photoelectrochemical energy-conversion devices.

Synthesis and Photophysical Properties of a Covalently Linked Porphyrin Chromophore–Ru(II) Water Oxidation Catalyst Assembly on SnO2 Electrodes

We describe here the preparation and surface photophysical properties of a covalently linked, chromophore-catalyst assembly between a phenyl phosphonate-derivatized pentafluorophenyl-substituted porphyrin and the water oxidation catalyst, [RuII(terpyridine)(2-benzimidazolylpyridine)(OH2)]2+, in a derivatized assembly of porph-RuII–OH22+. The results of nanosecond transient absorption measurements on nanoparticle SnO2 electrodes in aqueous acetate buffer at pH 4.7 are consistent with rapid electron injection into SnO2 with transfer of oxidative equivalents to the assembly. Electron transfer from the singlet excited state of the porphyrin to the conduction band of the electrode, SnO2(e–)|-porph+-RuII–OH22+, is favored as the porphyrin singlet excited state lies 0.44 eV above the SnO2 conduction band edge. Electron injection is rapid (⟨τinj⟩ < 10–8 s), and occurs with high efficiency. Based on measured redox potentials, following excitation and injection, intra-assembly oxidation of the catalyst, -porph+-RuII–OH22+ → -porph-RuIII–OH2+ + H+, is favored in the transient equilibrium state by 0.62 eV at pH 4.7. However, immediately after the flash, a distribution exists at the surface between isomers with SnO2(e–)|-porph+-RuII–OH22+ undergoing back electron transfer to the surface with an average lifetime of ⟨τ1⟩ ∼ 10–7 s and a slower component for back electron transfer from SnO2(e–)|-porph-RuIII–OH2+ with ⟨τ2⟩ ∼ 4 × 10–5 s.

Benzoporphyrins bearing pyridine or pyridine-N-oxide anchoring groups as sensitizers for dye-sensitized solar cell

Novel benzoporphyrins bearing pyridine or pyridine-[Formula: see text]-oxide groups were prepared through a concise method based on a Pd0 catalyzed cascade reaction. These benzoporphyrins were examined as sensitizers for dye-sensitized solar cells. Vicinal pyridine and vicinal pyridine-[Formula: see text]-oxide groups were introduced as new types of anchoring/acceptor groups for dye-sensitized solar cells for the first time. While all the porphyrins showed solar to electricity conversion, benzoporphyrins bearing pyridine-[Formula: see text]-oxide anchoring groups displayed higher conversion efficiency than benzoporphyrins bearing pyridine-anchoring groups.Opp-dibenzoporphyrins display broadened and red-shifted UV-vis absorption and emission bands as compared with those of the monobenzoporphyrins, which arises from the fusion of one more benzene ring and the attachment of two more electron-withdrawing groups to the porphyrin [Formula: see text]-positions. Cyclic voltammetry (CV) data and DFT calculation data obtained for these porphyrins agree well with their UV-vis absorption and fluorescence spectroscopic data. The HOMO energy level derived from the first oxidation potentials indicate that regeneration of the resulting porphyrin radical cation by the redox mediator (I[Formula: see text]/I[Formula: see text] is thermodynamically feasible for all these benzoporphyrin sensitizers (3, 5, 8 and 10). On the other hand, excited state energy levels of these benzoporphyrins calculated from the CV data, the UV-vis and fluorescence spectroscopic data are all slightly lower than the energy level of the conduction band of TiO2, suggesting insufficient driving force for efficient electron injection from the porphyrin excited singlet state to the conduction band of TiO2.

A π‐Stacked Porphyrin–Fullerene Electron Donor–Acceptor Conjugate That Features a Surprising Frozen Geometry

A "frozen" electron donor-acceptor array that bears porphyrin and fullerene units covalently linked through the ortho position of a phenyl ring and the nitrogen of a pyrrolidine ring, respectively, is reported. Electrochemical and photophysical features suggest that the chosen linkage supports both through-space and through-bond interactions. In particular, it has been found that the porphyrin singlet excited state decays within a few picoseconds by means of a photoinduced electron transfer to give the rapid formation of a long-lived charge-separated state. Density functional theory (DFT) calculations show HOMO and LUMO to be localized on the electron-donating porphyrin and the electron-accepting fullerene moiety, respectively, at this level of theory. More specifically, semiempirical molecular orbital (MO) configuration interaction (CI) and unrestricted natural orbital (UNO)-CI methods shed light on the nature of the charge-transfer states and emphasize the importance of the close proximity of donor and acceptor for effective electron transfer.

Preparation and Photophysical and Photoelectrochemical Properties of a Covalently Fixed Porphyrin–Chemically Converted Graphene Composite

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl-functionalized CCG and porphyrin boronic ester. The covalently linked CCG-porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady-state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin-linked CCG revealed a short-lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO(2) electrode coated with the porphyrin-linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π-conjugated systems in the excited and ground states.

Photoinduced Electron Transfer in Ruthenium(II)/Tin(IV) Multiporphyrin Arrays

The photophysical behavior of a series of heterometallic arrays made of a central Sn(IV) porphyrin connected, respectively, to two (SnRu(2)), four (SnRu(4)), or six (SnRu(6)) ruthenium porphyrin units has been studied in dichloromethane. Two different motifs connect the ruthenium porphyrin units to central tin porphyrin core, axial coordination via ditopic bridging ligands and/or coordination to peripheral pyridyl groups of the central porphyrin ring. A remarkable number of electron transfer processes (photoinduced charge separation and recombination processes) have been time-resolved using a combination of emission spectroscopy and fast (nanosecond) and ultrafast (femtosecond) absorption techniques. In these systems both types of molecular components can be selectively populated by light absorption. In all the arrays, the local excited states of these units (the tin porphyrin singlet excited state and the ruthenium porphyrin triplet state) are quenched by electron transfer leading to a charge-separated state where the ruthenium porphyrin unit is oxidized and the tin porphyrin unit is reduced. For each array, the two forward electron transfer processes, as well as the charge recombination process leading back to the ground state, have been kinetically resolved. The rate constants obey standard free-energy correlations with the forward processes lying in the normal free-energy regime and the back reactions in the Marcus inverted region. The comparison between the trimeric (SnRu(2)) and pentameric (SnRu(4)) arrays shows that all the electron transfer processes are faster in the latter than in the former system. This can be rationalized in terms of differences in electronic factors (due to the different connecting motifs) and driving force. In less polar solvents, such as toluene, the energy of the charge-separated states is substantially lifted, leading to a switch (from electron transfer to triplet energy transfer) in the deactivation mechanism of the excited ruthenium triplet.

Time-Resolved Thermodynamics of Inter-Molecular Electron Transfer Between Water-Soluble Anionic Free-Base Porphyrins and Ubiquinone

Inter-molecular electron transfer (ET) between ubiquinone (ubiQ) and biological molecules represents a critical process in cellular respiration. The biological importance of this process has stimulated research efforts to understand the fundamental mechanisms associated with proton-coupled ET involving ubiQ. In the present study the kinetics and time resolved thermodynamics associated with photoinduced intermolecular ET between the singlet states of two anionic porphyrins, meso-tetrakis(4-carboxyphenyl)porphyrin (4CP) and meso-tetrakis(4-sulfonatophenyl)porphyrin (4SP), and ubiQ are reproted. The anionic porphyrins facilitate charge separation between the porphyrin cation radical and the ubiQ anion radical. Addition of ubiQ to solutions of either 4SP or 4CP result in quenching of the porphyrin excited singlet state, τ(4SP/4CP)∼10-11ns and τ(4SP/4CP-ubiQ)∼8ns, with the quenching rate constants, kq, of 5x1010 M−1s−1 and 2x1010 M−1s−1 respectively. Time-resolved photoacoustic calorimetry (PAC) signals for both porphyrin species in the presence of ubiQ are monophasic (τ<50ns) with respect to a calorimetric reference at pH 9 and 7 and is independent of ubiQ concentration up to 1.4μM (initial concentration of 4SP/4CP ∼6-10μM). At pH 7 and 9 ΔV is independent of ubiQ concentration with a volume contraction of ∼2-3 mL mol−1 and expansion of ∼20 mL mol−1 respectively. Biphasic signals are observed for each species at pH 6: a fast phase <50ns and slow phase ∼300-400ns. The observed ΔH for the fast phase are independent of concentration within experimental error while those for the slow phase are reported as a function of ubiQ concentration.

Multiantenna Artificial Photosynthetic Reaction Center Complex

In order to ensure efficient utilization of the solar spectrum, photosynthetic organisms use a variety of antenna chromophores to absorb light and transfer excitation to a reaction center, where photoinduced charge separation occurs. Reported here is a synthetic molecular heptad that features two bis(phenylethynyl)anthracene and two borondipyrromethene antennas linked to a hexaphenylbenzene core that also bears two zinc porphyrins. A fullerene electron acceptor self-assembles to both porhyrins via dative bonds. Excitation energy is transferred very efficiently from all four antennas to the porphyrins. Singlet-singlet energy transfer occurs both directly and by a stepwise funnel-like pathway wherein excitation moves down a thermodynamic gradient. The porphyrin excited states donate an electron to the fullerene with a time constant of 3 ps to generate a charge-separated state with a lifetime of 230 ps. The overall quantum yield is close to unity. In the absence of the fullerene, the porphyrin excited singlet state donates an electron to a borondipyrromethene on a slower time scale. This molecule demonstrates that by incorporating antennas, it is possible for a molecular system to harvest efficiently light throughout the visible from ultraviolet wavelengths out to approximately 650 nm.

Naphthyl-Fused π-Elongated Porphyrins for Dye-Sensitized TiO2 Cells

Novel unsymmetrically π-elongated porphyrins, in which the naphthyl moiety is fused to the porphyrin core at the naphthyl bridge with a carboxyl group (fused-Zn-1) or at the opposite side of the phenyl bridge with a carboxyl group (fused-Zn-2), have been synthesized to improve the light-harvesting abilities in porphyrin-sensitized solar cells. As the results of π-elongation with low symmetry, Soret and Q bands of fused-Zn-1 and fused-Zn-2 were red-shifted and broadened, and the intensity of Q-band relative to that of Soret band was enhanced. The fused-Zn-1 and fused-Zn-2-sensitized TiO2 solar cells showed the power conversion efficiencies (η) of 4.1% and 1.1%, respectively, under standard AM 1.5 conditions. The η value of the fused-Zn-1 cell was improved by 50% compared to the reference cell using unfused porphyrin (Zn-1). The fused-Zn-1-sensitized cell revealed high IPCE (incident photon-to-current efficiency) values of up to 55%, extending the response of photocurrent generation close to 800 nm. Thus, the improved photocurrent generation of the fused-Zn-1-sensitized cell relative to the Zn-1-sensitized reference cell is responsible for the remarkable difference in the η values. The η value of the fused-Zn-2 cell was much lower than that of the fused-Zn-1 cell. DFT calculations disclosed that there are significant electron densities on the carboxyl group in the LUMO of fused-Zn-1, whereas there are little electron densities on the carboxyl group in the LUMO of fused-Zn-2. Accordingly, the larger electronic coupling between the porphyrin and the TiO2 surface in the fused-Zn-1-sensitized cell may be responsible for the high cell performance, due to the efficient electron injection from the porphyrin excited singlet state to the conduction band of the TiO2 electrodes. To further improve the cell performance, 5-(4-carboxylphenyl)-10,15,20-tetrakis-(2,4,6-trimethylphenyl)porphyrinatozinc(II) (Zn-3), possessing different light-harvesting properties, was coadsorbed with fused-Zn-1 onto an TiO2 electrode. Under the optimized conditions, the cosensitized cell yielded maximal IPCE value of 86%, short circuit photocurrent density of 11.7 mA cm−2, open-circuit voltage of 0.67 V, fill factor of 0.64, and η of 5.0% under standard AM 1.5 conditions.

Photoinduced Energy and Charge Transfer in Layered Porphyrin-Gold Nanoparticle Thin Films

In thin films of porphyrin (H2P) and gold nanoparticles (AuNPs), photoexcitation of porphyrins leads to energy and charge transfer to the gold nanoparticles. Alternating layers of porphyrins and octanethiol protected gold nanoparticles (dcore ∼3 nm) were deposited on solid substrates via the Langmuir−Schäfer method, forming bilayer films denoted as H2P/AuNP. Photoinduced electron transfer from the gold nanoparticle layer to the porphyrin layer was observed as a distinct photovoltage response of the H2P/AuNP film when studied via the time-resolved Maxwell displacement charge (TRMDC) method. Time-resolved fluorescence and absorption measurements of the H2P/AuNP film demonstrated a significant reduction of the lifetime of the excited singlet state of porphyrin caused by the gold nanoparticles. Transients of the charge transfer reaction were not observed in the time-resolved absorption measurements, which indicates that the quantum yield of the charge transfer is low in the H2P/AuNP film. Energy transfer from the excited singlet state of porphyrin to the gold nanoparticles is the main deactivation path of excited porphyrins in the H2P/AuNP film. The critical distance of the energy transfer was estimated to be 6.4 nm, based on the dependence of fluorescence quenching on the distance between the porphyrin and gold nanoparticle layers.

Light Harvesting and Energy Transfer in Multiporphyrin‐Modified CdSe Nanoparticles

Multiporphyrin-modified CdSe nanoparticles (CdSe-H2P) were prepared to elucidate the interaction between chromophores and luminescent semiconducting nanoparticles in the excited and ground states. The CdSe-H2P nanoparticles were obtained by place-exchange reactions of hexadecylamine-thiophenol-modified CdSe nanoparticles with porphyrin alkanethiols in toluene. The number of porphyrin molecules on the surface of a single CdSe nanoparticle increased with increasing reaction time to reach a saturated maximum of 21. The porphyrins as well as the core in CdSe-H2P can absorb UV/Vis radiation. Steady-state emission and emission-lifetime measurements reveal efficient energy transfer from the CdSe excited state to the porphyrins in the CdSe-H2P nanoparticles. The resulting porphyrin excited singlet state is not quenched by the CdSe core. These unique properties are in sharp contrast with those of multiporphyrin-modified metal and silica nanoparticles. Thus, semiconducting nanoparticle-multiporphyrin composites are highly promising as novel artificial photosynthetic materials.

Electrophoretic Deposition of Single-Walled Carbon Nanotubes Covalently Modified with Bulky Porphyrins on Nanostructured SnO2 Electrodes for Photoelectrochemical Devices

Single-walled carbon nanotubes (SWNTs) covalently modified with large porphyrin molecules have been prepared to construct photoelectrochemical devices with nanostructured SnO2 electrodes on which the multiporphyrin-linked SWNTs are deposited electrophoretically. The film of the porphyrin-linked SWNTs on the nanostructured SnO2 electrode exhibited an incident photon-to-photocurrent efficiency as high as 4.9% under an applied potential of 0.08 V vs SCE. The more uniform film and moderate photocurrent generation in the porphyrin-linked SWNT devices can be rationalized by the exfoliation abilities of the bulky porphyrins that yield large steric hindrance around the SWNTs. Direct electron injection from the excited states of the SWNTs to the conduction band of the SnO2 electrode is responsible for the photocurrent generation. Despite the efficient quenching of the porphyrin-excited singlet state by the SWNTs in the porphyrin-linked SWNTs, the photocurrent action spectra revealed that the excitation of the porp...

A Photoelectrochemical Device with a Nanostructured SnO2 Electrode Modified with Composite Clusters of Porphyrin-Modified Silica Nanoparticle and Fullerene

A silica nanoparticle has been successfully employed as a nanoscaffold to self-organize porphyrin and C60 molecules on a nanostructured SnO2 electrode. The quenching of the porphyrin excited singlet state on the silica nanoparticle is suppressed significantly, showing that silica nanoparticles are promising scaffolds for organizing photoactive molecules three-dimensionally in nanometer scale. Marked enhancement of the photocurrent generation was achieved in the present system compared with the reference system, where a gold core was employed as a scaffold of porphyrins instead of a silica nanoparticle. The rather small incident photon-to-current efficiency relative to a similar photoelectrochemical device using a silica microparticle may result from poor electron and hole mobility in the composite film due to poor connection between the composite clusters of a porphyrin-modified silica nanoparticle and C60 in micrometer scale.

Substituent Effects of Porphyrin Monolayers on the Structure and Photoelectrochemical Properties of Self-Assembled Monolayers of Porphyrin on Indium−Tin Oxide Electrode

Self-assembled monolayers (SAMs) of porphyrins have been prepared to examine the substituent effects of porphyrin monolayers on the structure and photoelectrochemical properties of the SAMs on an ITO electrode. The ultraviolet (UV)−visible absorption, steady-state fluorescence, and cyclic voltammetry measurements for the porphyrin SAMs revealed that the interaction between the porphyrins without bulky tert-butyl groups is much larger than that of the porphyrins with bulky tert-butyl groups. Photoelectrochemical measurements were performed in nitrogen-saturated Na2SO4 aqueous solution containing triethanolamine as an electron sacrificer using the modified ITO working electrode, a platinum wire counter electrode, and an Ag/AgCl reference electrode. The internal quantum yields of photocurrent generation together with the porphyrin fluorescence lifetimes remain virtually the same irrespective of the steric hindrance, which is in sharp contrast with severe self-quenching of the porphyrin excited singlet state in conventional molecular assemblies such as Langmuir−Blodgett films. The two-dimensional, densely packed structure of the porphyrins in SAM is responsible for the long-lived excited singlet state, which is similar to the antenna function of photosystem I in cyanobacteria. These results will provide valuable information on the construction of artificial light-harvesting systems.

Structure and Photophysical Properties of Porphyrin-Modified Metal Nanoclusters with Different Chain Lengths

Three-dimensional porphyrin-monolayer-protected gold clusters with different chain lengths (MPCs) have been prepared to examine the structure and photophysical properties, in comparison with self-assembled monolayers (SAMs) of the porphyrins on a flat gold surface. The three-dimensional porphyrin MPCs exhibit electrochemical and photophysical properties that are much closer to those of a porphyrin reference compound in solution than those of two-dimensional porphyrin SAMs on the flat gold surface. The three-dimensional architectures of porphyrin MPCs with large surface area have improved the light-harvesting efficiency relative to the corresponding porphyrin SAM on the two-dimensional flat gold surface. Time-resolved single photon counting fluorescence and transient absorption spectroscopic studies have demonstrated that undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three-dimensional MPCs is much suppressed, as compared to the quenching of the porphyrin SAMs on the two-dimensional flat gold surface. Both the quenching rate constants of the porphyrin excited singlet state by the surfaces of bulk gold and gold nanoclusters reveal weak chain length dependence of the energy transfer quenching.

Photovoltaic properties of self-assembled monolayers of porphyrins and porphyrin-fullerene dyads on ITO and gold surfaces.

A systematic series of ITO electrodes modified chemically with self-assembled monolayers (SAMs) of porphyrins and porphyrin-fullerene dyads have been designed to provide valuable insight into the development of artificial photosynthetic devices. First the ITO and gold electrodes modified chemically with SAMs of porphyrins with a spacer of the same number of atoms were prepared to compare the effects of energy transfer (EN) quenching of the porphyrin excited singlet states by the two electrodes. Less EN quenching was observed on the ITO electrode as compared to the EN quenching on the corresponding gold electrode, leading to remarkable enhancement of the photocurrent generation (ca. 280 times) in the porphyrin SAMs on the ITO electrode in the presence of the triethanolamine (TEA) used as a sacrificial electron donor. The porphyrin (H(2)P) was then linked with C(60) which can act as an electron acceptor to construct H(2)P-C(60) SAMs on the ITO surface in the presence of hexyl viologen (HV(2+)) used as an electron carrier in a three electrode system, denoted as ITO/H(2)P-C(60)/HV(2+)/Pt. The quantum yield of the photocurrent generation of the ITO/H(2)P-C(60)/HV(2+)/Pt system (6.4%) is 30 times larger than that of the corresponding system without C(60): ITO/H(2)P-ref/HV(2+)/Pt (0.21%). Such enhancement of photocurrent generation in the porphyrin-fullerene dyad system is ascribed to an efficient photoinduced ET from the porphyrin singlet excited state to the C(60) moiety as indicated by the fluorescence lifetime measurements and also by time-resolved transient absorption studies on the ITO systems. The surface structures of H(2)P and H(2)P-C(60) SAMs on ITO (H(2)P/ITO and H(2)P-C(60)/ITO) have been observed successfully in molecular resolution with atomic force microscopy for the first time.

Preparation of novel highly conjugated bis-porphyrin bridged with a polyene linker

This paper describes the preparation of a bis free-base porphyrin and a bis-zinc porphyrin system in which the two 5,10,15-tris(3,5-ditertbutylphenyl)porphyrinyl units are connected in meso position by a tetraenic chain. The preparation of the dyad relies on the Wittig-Horner-Emmons reaction between diethyl 3-[5-[10,15,20-tris(3,5-ditert-butyl-phenyl)-porphyrinyl]] prop-2-enyl phosphonate and the aldehyde-1,3-diene[5-[10,15,20-tris(3,5-ditert-butyl-phenyl)-porphyrinyl]]. The two latter porphyrin derivatives were obtained via a Stille cross-coupling reaction between the corresponding tributyltin derivatives and the 5-iodo-10,15,20-tris(3,5-ditert-butyl-phenyl)-porphyrin. The UV-visible absorption and fluorescence spectra of the bis-porphyrin systems are measured and indicate that both the energy level and the lifetime of the porphyrin singlet excited state are reduced upon the attachment of the polyene chain to the porphyrin unit.

C70 vs. C60 in zinc porphyrin-fullerene dyads: prolonged charge separation and ultrafast energy transfer from the second excited singlet state of porphyrin.

The second excited singlet (S2) state of porphyrin was efficiently quenched by the attached fullerene C70 moiety in a zinc porphyrin-C70 dyad. The quenching is largely explained by energy transfer to C70, but the possibility of additional reactions involving the S2 state of porphyrin is discussed. Singlet energy transfer was found to be an important decay pathway also for the first excited singlet (S1) state of porphyrin. In the polar solvent benzonitrile a charge-separated state was formed, and its lifetime was 890 ps, 50% longer than in the analogous porphyrin-C60 dyad.

Metal and size effects on structures and photophysical properties of porphyrin-modified metal nanoclusters

Three-dimensional (3D) porphyrin monolayer protected metal nanoclusters (MPCs) have been prepared to examine the effects of metal (Au, Ag, Au–Ag alloy, Pd and Pt) and size (1–3 nm) on the structures and photophysical properties. The quenching rate constants of the porphyrin excited singlet state by the surfaces of mono-metal nanoclusters and gold nanoclusters with different diameters are virtually the same. In contrast, the quenching rate constant of the gold–silver alloy nanocluster is half that of the corresponding mono-metal clusters (i.e. Au or Ag). This reveals that interaction between the surface of the gold–silver alloy and the porphyrin excited singlet state is attenuated as compared wtih the mono-metal systems. Thus, porphyrin metal alloy nanoclusters are potential candidates as a new type of artificial photosynthetic materials and photocatalysts.

Porphyrin Monolayer-Modified Gold Clusters as Photoactive Materials

Porphyrin monolayer-modified gold clusters (three-dimensional system) have been prepared successfully. Their electrochemical and photophysical properties have been compared to those of the corresponding two-dimensional system of self-assembled monolayers (SAMs) of the porphyrin as well as the bis(porphyrin) disulfide reference in solutions. In particular, the time-resolved single-photon counting fluorescence studies have indicated that the undesirable quenching of the porphyrin excited singlet state via energy transfer to the gold surface of the three-dimensional system is much suppressed, as compared to the quenching of the porphyrin SAMs on the two-dimensional flat gold surface. Thus, the present systems have a variety of potential utility for development of the artificial photosynthetic materials, photocatalysts, and chemical and biochemical sensors using fluorescent chromophore-monolayer modified gold clusters.